Process for dyeing mixtures of polyester and polyacrylonitrile fibers in one bath

ABSTRACT

PROCESS FOR THE SINGLE-BATH DYEING OF MIXTURES MADE OF POLYESTER AND POLYACRYLONITRILE FIBERS SIMULTANEOUSLY WITH DISPERSE DYESTUFFS AND CATIONIC DYESTUFFS ACCORDING TO THE TERMOSOL METHOD WHEREIN NON-IONIC DESPERSING AGENTS ARE ADDED TO THE ACIDIC PADDING BATHS WHICH CONTAIN THE CATIONIC DYESTUFF IN DISSOLVED FORM.

United States Patent Office Patented June 27, 1972 PROCESS FOR DYEING MIXTURES OF POLY- US. Cl. 8-21 A 6 Claims ABSTRACT OF THE DISCLOSURE Process for the single-bath dyeing of mixtures made of polyester and polyacrylonitrile fibers simultaneously with disperse dyestuffs and cationic dyestuffs according to the thermosol method wherein non-ionic dispersing agents are added to the acidic padding baths which contain the cationic dyestuff in dissolved form.

It is known that mixed materials from linear polyester fibers and polyacrylonitrile fibers can be dyed simultaneously with disperse and cationic dyestuffs according to the thermosol process.

In this method, the cationic dyestuffs may form addition compounds with the anionic dispersing agents used for disperse dyestuffs which may cause precipitation of the disperse dyestuff in the padding liquor, resulting in a distinct loss of colour yield and in uneven and specky dyeings.

In order to avoid such effects, it has been proposed to precipitate the cationic dyestuffs in the dyebath by means of anionic products and then to apply them onto the polyacrylonitrile fibers in analogous manner as the disperse dyestuff. For preventing the precipitation being coarsegrained it is necessary to add thickening agents to the padding liquor. This processhas the disadvantage that the fine distribution of the precipitated cationic dyestuffs can be controlled and reproduced with difficulty only and that the precipitation requires an additional process step. Furmore, the simultaneous use of thickening agents causes considerable soiling of the drying apparatus usually employed in the thermosol process and essentially reduces the properties of fastness, especially the fastness to rubbing and to washing, of the dyeings.

In mixtures which contain, besides polyester and polyacrylonitrile fibers, also cellulose fibers, the application of thickening agents results in a strong staining of the cellulose fiber portion by the disperse dyestutf, which has a negative influence on the fastness to rubbing and to washing of the dyeing.

Finally, thickening agents which cannot be removed by washing after the thermosol process impart onto the goods, in addition, a hard handle. Thus, it is almost impossible to obtain an even and speck-free dyeing with this process.

Now, we have found that the above-described disadvantages in the dyeing of mixtures of polyester and polyacrylonitrile fibers in one bath with disperse and cationic dyestuffs according to the thermosol process can be overcome by adding non-ionic dispersing agents to the acid padding liquors which contain the cationic dyestufi in dissolved form.

As non-ionic dispersing agents, there may be used according to the invention either polyglycols, oxyethylated oxazoline derivatives or oxalkylated fatty acid derivatives or mixtures of these products.

Among the suitable polyglycols, there may be used in particular polyethylene glycols having an average molecular weight in the range of from 1500 to 8000, especially those having a molecular weight of about 6000.

As oxalkylated fatty acid derivatives, there may be used according to the invention products which are derived from fatty amines, fatty acid amides or fat alcohols, preferably the oxethylation products of fat alcohols and fatty amines having polyether chains that correspond to 12 to 25 mols of ethylene oxide or mixtures of these compounds having a different degree of oxethylation, the reaction products of 1 mol of stearyl alcohol and 25 mols of ethylene oxide or of 1 mol of oleyl alcohol and 22.5 mols of ethylene oxide or of 1 mol of stearyl alcohol and 12 mols of ethylene oxide showing the most favourable behaviour.

As oxethylated oxazoline derivative, the reaction prod not of 1 mol of 2-heptadecyl-4-ethyl-4-hydroxymethyl-oxazoline and 70 mols of ethylene oxide is preferably used.

The mixture obtained from the reaction product of 1 mol of stearyl alcohol and 25 mols of ethylene oxide, polyethylene glycol having a molecular weight of about 6000, and the reaction product of 1 mol of Z-heptadecyl- 4-ethyl-4-hydroxymcthyl-oxazoline and 70 mols of ethylene oxide in a mixing proportion of 1:1:1 to 8:122, preferably 4: 1: 1, has proved especially favourable for the process of the invention. In general, 20 to 40 g., preferably 25 to 35 g., of non-ionic dispersing agent are added per liter to the padding liquor.

As disperse dyestuffs, there may be used according to the invention the dyestuffs usually employed for the dyeing of fibrous materials of linear polyesters, for example those of the series of azo or anthraquinone dyestuffs. Disperse dyestuffs of said type are known, for example, from Colour Index, second edition (1956), vol. 1, pages 1659- 1742 and Supplement (1963), pages S 179-S 22-4 as well as from the corresponding Additions and Amendments No. 1 (September 1963) to No. 26 (January 1970).

Among the cationic dyestuffs used according to the invention, there may be especially mentioned those of the series of azo, azomethine, methine, anthraquinone, nitro, diand triphenylmethane, phenazine, oxazine, thiazine, xanthene and quinophthalone dyestuffs. Suitable cationic dyestuffs are described in Colour Index, second edition (@1956), vol. 1, pages 1617-1653 and in Supplement (1963), pages S 149-8 177 as well as in the corresponding Additions and Amendments No. 1 (September 1963) to No. 26 (January 1970).

As free acid which, according to the invention, increases the solubility of the cationic dyestuffs in 'water, there may be used organic acids, for example acetic acid and formic acid, preferably acetic acid.

The process of the invention is carried out by applying onto the textile material of polyester and polyacrylonitrile fibers an aqueous preparation having a temperature of from 20 to 40 C., preferably 30 C. and containing, in addition to dispersed disperse dyestuffs and dissolved cationic dyestuffs, free acid and non-ionic dispersing agents.

In order to prepare the padding liquors, the cationic dyestuff is first pasted up with the acid and dissolved by the addition of boiling hot water. After cooling to 20 to 40 C., this solution is added to an aqueous dispersion of the disperse dyestuffs having a temperature in the range of from 20 to 40 C. and to which a mixture of non-ionic agents had previously been added.

Following the padding process, the wet mixed material is dried at a temperature in the range of from to 130 0., preferably at C., and then subjected to a heat treatment for 30 to 90 seconds, preferably 60 seconds, at 180 to 210 C., preferably at 200 C., by means of hot air, superheated steam, a mixture of heated air and superheated -steam or on heated cylinders, during which time the disperse dyestutf is fixed onto the polyester fiber and the cationic dyestufl is fixed onto the polyacrylonitrile fiber. This heat treatment simultaneously fixes the polyester portion of the mixed material and imparted its optimal technological properties.

After this dyeing process, the goods are rinsed and soaped and further treated in the usual manner.

It is noteworthy that in the process of the invention the addition of the non-ionic dispersing agents provides a good stability of the padding liquors containing disperse and cationic dyestuffs and that, with interesting bicolour eflects, even and speck-free dyeings are obtained with a very good colour yield and good general fastness properties. Finally, it was surprising that, in contradistinction to the opinion of experts, anegative influence on the textile-technological properties of the polyester fibers is not exerted by the auxiliary agents at the elevated temperatures used according to the invention.

The textile material to be dyed according to the present invention, which consists of mixtures of linear polyesters,

preferably polyethylene terephthalate, and polyacrylonitrile fibers, alone or in admixture with native or regenerated cellulose fibers, may have the form of a yarn, fabric or knitted fabric.

In the case of mixed materials which contain, in addition to polyester and polyacrylonitrile fibers, also cellulose fibers and in which the individual components are present in the ratio of 1:1:1, the cellulose fiber portion of the goods is dyed with dyestuffs of the classes usually employed for cellulose fibers, especially reactive dyestufis, according to the methods known for these purposes, after the heat treatment, without/ or after previous intermediate cleaning.

The dyestuffs used in this further embodiment of the process of the invention are, preferably, such organic compounds which contain at least one group capable of reacting with the cellulose fiber, a precursor for such a group or a substituent capable of reacting with the cellulose fiber. The parent components of these dyestuffs may belong to difierent classes of compounds; particularly suitable are those of the series of the anthraquinone, azo and phthalocyanine dyestuffs; the azo and phthalocyanine dyestuffs may be metal-free or metalliferous. Within the group of these dyestuffs, the reactive groups and precursors, which form such reactive groups in an alkaline medium, are, for example epoxy-groups, the ethyleneimide group, the vinyl group within the vinyl-sulfoneor acrylic acid radical, furthermore the ,B-sulfato-ethyl-sulfonyl group, the B-chloroethyl-sulfonyl group, the B-thiosulfato-ethyl-sulfonyl group, the fi-phosphatoethyl-sulfonyl group. It is in this connection without importance whether the aforementioned radicals are connected directly or over an intermediate member, especially NH- or --NR (R=1ower alkyl) to the dystuif molecule, as, for example in the case of the ethionyl-amino radical. Reactive substituents in reactive dyestufis may also be such substituents which are easy to split off and which leave behind an electrophilic residue. IAS examples of such substituents, there may be mentioned halogen atoms at the following ring systems: quinoxaline, triazine, pyrimidine, phthalazine and pyridazone. Examples of re- -active dyestuffs of the kind cited above are described in US. Pats. Nos. 2,670,265 (vinylsulfone, sulfatoethylsulfone and phosphatoethylsulfone); 2,657,205 (vinylsulfone); 3,197,456, 3,349,097, 3,324,151 and 3,261,823

HzN riH-oHPon and 11 g. of the disperse dyestutf (Color Index No. 26080) of the formula 3 g. of the disperse dyestufi (CI. 26080) (US. Pat. No. 3,125,402) of the formula OKs-CHz-O-CO-CH;

8 g. of the cationic dyestulf (US. Pat. No. 2,906,588) of the formula I e 6 0-0 H=C H-N Cl 16 g. of the cationic dyestufi (French Pat. No. 1,597,864) of the formula and 12 g. of the cationic dyestutf (German Pat. No. 1,011,396) of the formula on osm (British Pat. 855,153) in commercial form and composi- EXAMPLE 3 and A mixed fabric of polyethylene terephthalate fibers and 24 g. of the reaction product of 1 mol of stearyl alcohol polyacrylonitrile fibers in a mixing ratio of 50:50 was and 25 mols of ethylene oxide, padded on the foulard with a squeezing effect of 50% 6 g. of a polyethylene glycol having a molecular weight 5 Weight increase, with a bath having a temperature of 20 of about 6000, C. and containing, per liter of water, 60 g. of the disperse 5 g. of the reaction product of 1 mol of 2-heptadecyl-4- dyestuff (US. Pat. No. 3,367,937) of the formula ethyl-4-hydroxymethyl-oxazoline and 70 mols of ethyl- 0 ene oxide, and k 20 cc. of acetic acid (60% strength). NCH CH-.-CH OCHa The padded fabric was then dried for 40 seconds at 100 C. and subjected to a heat treatment with heated air for 60 seconds at 200 C. and g of the cationic dyestuif (German Pat. No.

The dyeing was then rinsed hot and cold in the usual 1,011,396) of the formula S CHz-CH NC a CH: manner, soaped with a solution containing, per liter of in commercial form and composition, and water 2 of a non'lomc surfaccactwe agent rinsed 24 g. of the reaction product of 1 mol of stearyl alcohol again and worked up. and 25 01 f th 1 A fabric was obtained in which the polyester and poly- 25 m s o e y me OX1 acrylonitrile portions were dyed black tone-in-tone. If 6 gig g gg glycol havmg a molecular welght the dyeing is carried out according to the above-described method, but without the non-ionic dispersing agents of the invention, a dyeing is obtained which is uneven and fi g; i gig oxazolme and 70 mols of m which the colour yleld 1s markedly lower. 20 cc. of acetic acid (60% Strength) EXAMPLE The padded fabric was dried for 40 seconds at 100 C.

A mixed fabric consisting of polyethylene terephthalate and then subjected for 60 seconds to a treatment with hot fibers and polyacrylonitrile fibers in a ratio of :50 was air at 200 C. The dyeing was then completed in the padded on the foulard with a squeezing eifect of 50% 35 usual manner.

5 g. of the reaction product of 1 mol of 2-heptadecylby weight, with a bath having a temperature of 20 C. A fabric was obtained in which the polyester fiber porand containing, per liter of water, 30 g. of the disperse tion was dyed yellow and the polyacrylonitrile fiber pordyestufi (Belgian Pat. No. 636,010) of the formula tion was dyed red.

EXAMPLE 4 I /CH2 CH2 O CO CH3 40 A mixed fabric of polyethylene terephthalate fibers, Q Q polyacrylonitrile fibers and fibers of regenerated cellulose CHa-CHr-O-CO-CH: in a. mixing ratio of 33:33:33 was padded on the foulard and 20 g. of the cationic dyestufi (German Pat. No. with a squeezing effect of 65% weight increase, with a 1,011,396) of the formula bath having a temperature of 30 C. and containing, per

N=NN 0 H3 CH3 0 S 0 9 S/ 83H; cnrcnri c Ha CH3 in commercial form and composition, and liter of water, 30 g. of the disperse dyestuff (Belgian Pat.

16 g. of the reaction product of 1 mol of stearyl alcohol 636010) of the formula and 25 mols of ethylene oxide, CN 4 g. of a polyethylene glycol having a molecular weight /CHZ"CHZ OCO CH of about 6000, om -N=N -N 5 g. of the reaction product of 1 mol of 2-heptadecyl- 4-ethyl-4-hydroxymethyl-oxazoline and 70 mols of CHrCHrO CO ethylene oxide, and and 20 g. of the cationic dyestufl? (German Pat. No.

1,011,396) of the formula 20 cc. of acetic acid (60% strength).

in commercial form and composition, and

The Padded fabric was then subjectefi withoflt inter 24 g. of the reaction product of 1 mol of stearyl alcohol mediate drying, to a treatment for 2 minutes with satuand 5 mols f ethylene oxide rated steam at 125 C. The dyeing was then completed 6 g. of a polyethylene glycol having a molecular weight a1 of about 6000,

i d h th as f 01 5 g. of the reaction product of 1 mol of 2-heptadecyl -4- yemg was 0 m w w 6 por 1o 0 p ethyl-4-hydroxymethyl-oxazoline and 70 mols of ethylester and polyacrylonitrile fibers were dyed red tone-mene oxide, and

tone. 7 7 H 20 cc. of acetic acid (60% strength).

ocrr,

S OCHrCHzO-SO;Na

SO Na and 2 g. of the reactive dyestufi (German Pat. No. 1,150,-

163) of the formula den;

in commercial form and composition, and

12 cc. of sodium hydroxide solution (32.5% strength),

and 30 g. of calcinated sodium sulfate.

The padded material in rolled up state was left to dwell for 6 to 8 hours at room temperature. The fabric was then rinsed in the usual manner, with a solution containing, per liter of water, 2 ml. of a 60% acetic acid, acidified, rinsed again, soaped with a bath containing, per liter of water, 2 g. of a non-ionic surface-active agent and completed.

A fabric was obtained in which the portions of polyester, polyacrylonitrile and regenerated cellulose fibers were dyed red.

We claim:

1. A process for the dyeing of a textile material made of a mixture of polyester fibers and polyacrylonitrile fibers simultaneously with a disperse dyestufi and a cationic dyestuff according to the Thermosol method which comprises padding said textile material with a padding bath consisting essentially of said cationic dyestufl in dissolved form, said disperse dyestufl, a low molecular weight alkanoic acid and a dispersing agent that is a mixture of polyalkylene glycol, a long-chain alkyloxazoline reacted with alkylene oxide and a fatty amine, fatty acid amide or fatty alkanol reacted with alkylene oxide, and thermosoling the padded material to fix said cationic dyestufi on said polyacrylonitrile fibers and said disperse dyestuff on said polyester fibers.

2. A process according to claim 1 wherein said polyalkylene glycol is a polyethylene glycol having an average molecular weight in the range of 1500 to 8000.

3. A process according to claim 2 wherein said polyethylene glycol has an average molecular weight of about 6000.

4. A process according to claim 1 wherein said dispersing agent is a mixture consisting of the reaction product of 1 mol of stearyl alcohol and 25 mols of ethylene oxide, a polyethylene glycol having a molecular weight of about 6000 and the reaction product of 1 mol of 2 heptadecyl 4 ethyl 4 hydroxymethyl-oxazoline and mols of ethylene oxide in a mixing ratio range of 1:1:1 to 8:1:2.

5. A process according to claim 4 wherein said mixing ratio is about 4:1:1.

6. A process according to claim 1 wherein said dispersing agent is added in an amount of about 20 to about 40 grams per liter of said padding bath.

References Cited UNITED STATES PATENTS 3,436,169 4/1969 Zurbucher 8173 X 3,391,985 7/1968 Zurbucher 8-174 X 2,764,466 9/1956 Bigood 821 A 3,096,139 7/1963 Hindle 8-21 R OTHER REFERENCES Du Pont Textile Fiber Technical Information, Multi- Fiber, Bulletin X-100, February 1959, 4 pages. 1 Mayer, Melliand Textilberichte, pp. 500-503, May

Schwartz, Peray, and Berch: Surface Active Agents and Detergents, vol. II, pp. 108-11, pub. 1958 by Interscience Pub., Inc., New York, N.Y.

DONALD LEVY, Primary Examiner US. Cl. X.R. 8-21 C, 172, 173 

